A CURABLE POLYSULFIDE POLYMER COMPOSITION

Abstract: The invention relates to a curable polysulfide composition, which has an application in making a preserving coating, and an insulator in the field of road construction, house building, etc. The target of the invention is to obtain a stable polysulfide curable composition for which the cure rate and the cure velocity are independant of the surroundings, to allow the obtaining of vulcanized material with high grade of technical and ecological parameters, avoiding the typical unpleasant smell of mercaptane polysulfides and the toxicity of the curing agents, additives and fillers. The problem is solved using the following curable polysulfide composition: polysulfide polymer and/or copolymer containing up to 1 mol/kg SH groups, with molecular weight from 2,000 to 200,000, polysulfide degree from 2.2 to 4.0, ramification rate up to 4 mol percent and degree of polymerization of 20 to 500 in an amount of 90 to 110 pbw and having the average formula (I); modifier up to 75 pbw; curing agent from 0.2 up to 20 pbw; polar solvent or reagent up to 25 pbw; acceptor from 5 to 50 pbw; fillers and other additives up to 150 pbw.

Description: A CURABLE POLYSULFIDE POLYMER COMPOSITION The invention relates to a curable polysulfide composition suitable for use as an insulator and filler (gap compensator) in road and house building and a means of binding various details in automobile and airplane construction, hermetical sealing, impreg¬ nating porous materials and preparing corrosion, hydro and thermo resistant coatings and caulkings. A composition is known that is self-curing under atmospheric conditions after application on a surface. This mixture comprises a liquid polysulfide mercaptan group-terminated polymer (molecular weight 4000, cross-linking 0.5%, mercaptan groups 0.53 mol/kg), a peroxide of an alkaline or alkaline earth metal as a watersoluble curing agent, an alkaline or alkaline earth oxide, hydroxide or salt of a weak acid as a water-soluble activating agent as well as other modifying additives and fillers I I. Drawbacks of the composition: the curing agents are highly inflammable and unstable peroxide compounds; the curing rate is unpredictable since it depends directly on the moisture present in the air; the presence of mercaptan groups in the polymer imparts an unpleasant smell to the composition and may provoke cyclic polycondensation or preliminary curing during the storage. A curable composition is known to those skilled in the art as well as a method of curing this composition 121 , which consists in mixing at ambiant temperature of: (a) polysul fide polymeric latex zw-679 (10-20 pbw) which represents an aqueous dispersion contain- ing about 60% of a solid phase linear polymer, with a molecularweight of 100 000 and the general formula. -/R - S χ /n-, wherein S is a polysulfide linkage, R is oxahydrocarbon, n is about 500; (b) a polyurethane prepolymer (15-30% of the total amount of the mixture and 4-10% isocyanate groups); (c) fillers; (d) plasticizers; (e) a latex stabilizer and (f) an antisponging agent. A disadvantage of this composition is that no real curing (cross-linking) of the polysulfide polymer occurs because the composition contains neither branches along the linear chain nor mercaptan groups by means of which curing or cocuring with the polyurethane copolymer would occur. Besides, the composition con¬ tains no curing agent, in fact the mixture harden as a result of hydrolysis of the isocyanate groups of the polyurethane under the effect of the water of the latex dispersion, while the polysulfide polymer densifies by coalescence without cross-linking and, as a result, a series of the properties of the cured product are not good enough. A polysulfide polymer is known /3/ which has a molecular weight of 3000 to 100 000 and the general formula Y " < S n R J ffl S n " Y L [(S n R') lSn - Y] p wherein R and R' are independent polyvalent organic radicals, Y is a terminating inert monovalent substituent, m is a positive integer n ranges from 2 to 8, and p and 1 are equal to zero or are positive integers. The drawback of this polysulfide polymer is that it is used as a plasticizer only. The target of the invention is to obtain a stable polysulfide curable composition for which the cure rate and the cuure velo city are independent of the moisture content of the surroundings and the resulting cured composition has high technical properties including in cases when polysulfide polymers containing no mercap¬ tan groups used, has a wide sphere of application and is ecologi¬ cally and economically favourable. This problem is solved using the following curable polysul¬ fide composition: A polysulfide polymer and/or copolymer having up to 1 mol/kg SH groups, a molecular weight of 2000 to 200 000, a sulfur rank of 2.20 to 4.00, cross-linking ranging from 0 to 4 mol%, a degree of polymerisation of 20 to 500 in an amount of 90 to 110 pbw, and the general formula R l " ' a→ R Vy - 'f " /R " " /R ' " 'Va a *T R 2 t s x R ι - 8 Λ, " R 3 ι b wherein S is a sulfur atom S is a divalent polysulfide or monosulfide radical x is an integer ranging from 1 to 6 a., a. and a. are the same or different and have values of 0 to 1 y denotes the number of monomer unit and the number of polysulfide bonds in the polysulfide segment of a given polysulfide copolymer with values varying between 1 and 10 y' is the number of monomer links connecting the poly¬ sulfide and nonsulfide segments of a given copoly mer and has values of 0 or 1 y* stands for the number of monomer links in the non¬ sulfide polymeric segment and has values of 0 to 5 z is the degree of polymerization of the polysulfide 1 has values of 0 to 5 b denotes the number of polysulfide branches of the linear polymer chain or the copolymer, respectively, formed by the binding and chain branching polyva¬ lent monomer, and is equal to R' minus 2 R is a saturated divalent normal or isoalkyl, aralkyl or aril radical, wherein the alkyl radical or the alkyl part of the aralkyl radical is a hydrocarbon, oxahydrocarbon or thiahydrocarbon, and the group being illustrated more precisely by the following formulas: -Cn_H2,n-; -C Λ 6H4,-; -CnH2-nOCnH2-n-; -CnH2.nSCnH2,n-; -C6J4.OCnH2,n-? -CnH,2nC6,H4.OC6J4.CnH2,n-; -C 6 H 4 0 C m H 2ffi O/ f C 6 H 4 -; -C 6 H 4 C n H 2n OC n H 2n C 6 H 4 - ; - C n H 2n 0 C m H 2m 0 f C n H 2n " ' ~ C n H 2n OC 6 H 4 OC n H 2n- ' CH, -CH 0CH.CCH_0CH - ; -CH 2 -CH-CH 2 ~ ; 2 2 i . 2 - CH 2-?6 H 3- CH 2- ' CH, CH, C 6 H 5 -cellulose-OCH 2 COO-; CH 3 -< - C n H 2n -Si/OC m H 2ιn+1 3 ; wherein n ranges from 1 to 24 m ranges from 1 to 5 f ranges from 1 to 10 R', R*, R" and R 1 * are the same or different saturated monovalent hydrocarbon, oxahydrocarbon or thia- hydrocarbon radical R τ is a saturated monovalent alkyl radical of the kind ~ SC m H 2m+l ° r - 0C m H 2 + r' is a polysulfide linkage; x ranges from 3 to 5. R. R 2 and R 3 are the same or dif erent terminals representing normal or iso-alkyl, aryl or aralkyl radicals Or groups of the type: -SH; -SSH; -OH; -CHO; -C n H 2n+1 -C n H 2n C 6 H 5 ; - C 6 H 4 S 6 H 5' -OCAn+l' -° C 6 H 5 Ϊ ~ C n H 2n 0H ' - C 6 H 4 OH ' -° C 6 H 4 C 6 H 4 OH ' -° C n H 2n 0H ' -0/C nH 2,n/ m: -NHC '6.H"5-; -CH-CH,; -CH-CH_-CH-CH_; \/ 2 ' 0 OH 2 ~ \ 7 '2 R° R° \ -C nH 2,n-S , i-R° -C nH 2,n /OC siH.2m/.1-S .Ϊ-R" R° -CH.-CHCH,/OC H. Λ -Si-R ∞ ; OH R°°° wherein R°° and R°∞ are the same or different saturated monovalent radicals of the group: -OC H„ __, ; τa 2m+l ' -OC H- C C H_ or -C H Λ m 2m 6 5 m 2m+l n has values from 1 to 10 m has values from 1 to 5 1 has values from 1 to 10 R ιv is a polyvalent radical with a weight up to 10 % from the molecular weight of the said polymer or copolymer and is a radical of a polyfunctional com pound selected from the group: XR j X 2 ; XCH^HXR^CHXC^X R^-CX^ ^ * 4 ' C \H2_-/CHCH 2„X; O X H X 0 H I > X-C-C-OH X-C •-C ✓ X-C-X ; I i I \ X H X H R ooo _Si-R° I R ∞ wherein X is a halogen atom R n and JJJ are hydrocarbon, oxahydrocarbon, thia- hydrocarbon or aralkyl radicals is selected from the group consisting of alkyl, aryl, aralkyl radicals or is a carbon atom R VI , R^ J , R TIII and R IX are alkyl radicals representing a hydrocarbon or oxahydrocarbon R ° . R∞ aiX d OOD are tne same or different monovalent radi ¬ cals of the group: -OC m H 2m+1 -C n H 2n C 6 H 5 ; -OC 6 H 5 , wherein w * ranges from 1 to 5 and ,"n M ranges from 1 to 10 represents a saturated divalent radical free of SH, SSH and S groups and is selected from the group: -CH -CH-CH - ; -CH 2 -CH- ; -CH.-CH- ; 2 I 2 I OH CN C 6 H 5 -CH,-CH,CH,OCH,CH,CH,Si/OC m H 2m / 2 - -CH-CH- OCH 2 C 6 H 5 ' CH 2 - OCO-HN NH-COO/CH,/. OCH -CH-CH 1 H <), H,C- -KHCOO/CH 2 / 2 OCONH -CH, <^> < £ > • O -CH 2 - CH 2 - wherein m has values from 1 to 5 1 1 has values from 4 to 6 1 2 has values from 4 to 6 R° and R°° are the same or different having the corre¬ sponding meaning of R°, R°°, R 000 included in R, or they are hydrogen atoms or alkyl radicals. The composition contains up to 75 pbw modifiers. A low-mole¬ cular polysulfides polymer free of SH and SSH groups with a molecular weight of up to 2000, a degree of polymerisation of 2 to 10, and a sulfur rank of 2.5 to 5 is used as modifier and plasti- cizer. It is illustrated by the general formula: R.1-/Sx/a—F l -RSx-Γ J y-R2_, wherein is a polysulfide linkage x has values ranging from 2 to 6 y has values from 3 to 10 a is from 0 to 1 R, R. and R- have the meanings given for the main polymer and/or copolymer excepting -SH and -SSH. Other modifiers used are polysulfide dimers of the kind wherein S is a polysulfide bond x has values between 3 and 6 R is a saturated monovalent radical free of SH and SSH groups and is selected from the group _J / ^ CH.-CH-R- -C-N •• \ OH S R„ *C I -0CmH2_m+_l /CH 2 / 1 0H -CH • 2.-C,H-R"_7-0-R,-S ri-R°° ; -Ar-R.-Si-R 00 ; 7 OH R Iooo R° wherein R 1 to R χ4 denote alkyl or aralkyl radicals containing from 1 to 15 carbon atoms; R°, R°° and R 000 are the same or different saturated monovalent radicals of the kind " 0C m H 2m + l ' -∞AaVs ' "C 6 H 5 ' "C m H 2m+l ' wherein m has values from 1 to 5 1 has values of 1 to 5 p has values of 1 to 5 Ar is an aryl radical Or R belongs to the group of benzothiazoles or another modi¬ fying group. Another possible modifier is a polysulfide monomer with the formula wherein S is a sulfur atom S is a polysulfite bond is an integer with values of 3 to 6 v 1 » R 2 , R 3 and R 4 are the same or different modifying monovalent radicals having the meaning of any R radical or the R radical of the polysulfite dimer given above or are other modifying radicals free of SH and SSH groups. The modifying additive may also be hydrolizable poly- urethane/prepolimer containing free isocyanic groups (5 - 40 mol %) or another hydrolyzable polymer or a nonsulfide polymer able to cocure with the polysulfides of the composition or another nonsulfide copolymer able to copolymerize with a mercaptan group-terminated polymer of the composition. The composition also contains 0.2 to 20 pbw of a curing agent comprising, or creating, under the effect of the polar agent, active ions or active molecular centers able of curing the polysulfite components, being consumed once or regenerated many times. The curing agent used is a chemical element or a chemical compound which interacts and/or is dissolved in liquid or gaseous (at the curing temperature) polar reagent and/or polar solvent, and is selected from the group: gaseous substances such as NH_, CO, COS, 0-, diborane, hydrogen selenide, methylamine, trimethylamine, etc; metal powders such as Li, Na, K, Ba, Cd, Mή, Pb, Sr, Zn etc; hydroxides such as NH 2 OH, NH OH as well as the hydroxides of Li, K, Na, Ba, Ca, Be, Zn, etc; oxides of Li, K , Na, Ba, Ca, B, Pa, Sb, Cr, Mn, Sn, Te, etc; Salts of metal acids (double oxides) such as antimonates, bismuthates, borates, vanadates, tungstates, perman¬ ganates, molybdates, plumbates, selenides, selenates, silicates, ferates, tellurates, chromates, bichromates, zincates etc; monosulfates of ammonia, Ma, K, Li, Ba, Ca, Mg, Si, B, Ti etc; metal pyro phosphates; etal amides; metal alcoholates; metal mercaptides and polimercaptides; alkaline catholytes; alkalized chloro paraf¬ fins, salts of saturated fatty and aromatic mono and dicarboxylic acids as well as of the methylbenzoic, phenylacetic, terephtalic acids; hydrazine and organic hydrazines; polymeric metal alcoholates and carboxylates, metal-containing hydrocarbons etc; organic amides and amines including benzoxazoles, benzthiazoles, benztriazoles and alkylthiurams or the curing agent is insoluble in the given polar solvent and is a metal powder, oxide, hydroxide, or oxyhydroxide whose metal has a higher chemical affinity to sulfur than to oxygen, or the curing agent is a polar liquid or a polar melt or an unsaturated low-molecular organic compound. The composition also contains up to 25 pbw of a polar reagent and/or a polar solvent which, at ambient temperature, is mainly water, alcohol, a liquid organic acid or another polar reagent and/or solvent and at elevated curing temperature it is mainly a saturated higher fatty acid or another polar organic reagent and/ or polar solvent which is liquid at this temperature. The composition also contains 5 to 50 pbw of an acceptor which can be: an acceptor of a gaseous polar reagent and/or a solvent (mostly acceptor of moisture) and represents an organic liquid infinitely soluble in the polar solvent or the said acceptor is a highly hygroscopic powdery potential curing agent: BaO, Na 2 0, Na, etc; an acceptor of sulfur, containing mainly Sb, Be, Bi, V, w, Fe, Hg, Sn, Co, Mn, Cu, MO, Ni, Pb, Zn etc; an acceptor of C0 2 : mainly Mg(OH) and Zn(OH) ; an acceptor of acid anions: e.g., mainly MgO and ZnO for SiO *-. Up to 150 pbw of fillers (known special-purpose additives and inertllers) and with some compositions, also gasforming fillers and/or ^active" fillers such as soot, molecular sieves, zeolites, etc. are added. THE INVENTION HAS TEE FOLLOWING ADVANTAGES: l.The composition allows to cure polysulfite polymers with no mercaptan content. 2.The hygiene of the working conditions is improved during both the preparation and the application of the composition. 3.The composition permits the introduction of considerable amounts of water, which plays multifunctional role: a dispersing agent for hygroscopic components (e.g. ZnO); a solvent and ionizer of the curing agent; a means for decreasing the viscosity of the composition, improving its homogenization and decreasing the amount of attracted air (i.e. the air bubbles in the cured material). The water also takes part as a structural water in the cured composi¬ tion, saturating the free valencies liberated during the curing, and this reduces or completely eliminates the volume swell of the cured material when placed in water or another solvent, i.e. the chemical stability and the dimensional precision of the cured composition increase, while its cost price decreases. 4. The curing agents are not inflammable and unstable per¬ oxides. Besides, their large number allows the best choice for each composition and enlarges the application field of the compo¬ sitions. 5. Tyhe modifiers used, some of which play also the role of plasticizers, copolymerize or are co-cured along with the main polysulfide polymer or copolymer, as a result of which they can not be washed off and do not evaporate. 6. When a one-pack curable composition is prepared for a gaseous curing agent, no preliminary drying of the components and no evacuation or hermetic closing of the composition in the ves¬ sels, where it will be stored, is needed. The whole necessary water amount is introduced previously and the cure rate and cure velocity become independent of the amount of moisture in the surroundings. The following examples are intended to be merely illustrative of the present invention and not in limitation thereof. EXAMPLE 2 The one-pack prepared composition consists of: 100 pbw of an epoxy-polysulfide polymer having epoxy-termi- nated groups, an average sulfur rank of 2.2, with no cross-linking and the average formula: H-C-CH-CH.-S-R-S-CH--CH-CH_, 2 \/ 2 2 \/ 2 O 0 wherein R = -/CH 2 CH 2 OCH 2 S χ / 6 CH 2 CH 2 OCH 2 CH 2 - x has values of 2, 3 or 4 1 pbw of powdered sodium or 2 pbw of powdered sodium hydroxid as an acceptor of moisture and dormant curing agent 10 pbw of zinc oxide as an acceptor of sulfur and filler 5 pbw of glycerol as an acceptor of atmospheric moisture, inhibitor of curing and struc¬ ture-forming agent 5 pbw of Ti0 2 as a neutralizing agent (acceptor of excess of alkalinity). The composition is cured upon reaction with atmospheric mois¬ ture. EXAMPLE 2 A curable composition consisting of: 100 pbw of a liquid polysulfide polymer (LP-32C) whose SH groups have been blocked by pre-treatment with HS-CH 2 CH -OH 15 pbw of water as a solvent of the curing agent and a structure forming agent. 12 pbw zinc oxide as acceptor of sulfur The mixture is homogenized well. At first aqueous suspen¬ sion of the zinc oxide is prepared and added to the liquid polymer. The curing proceeds under the effect of gaseous ammonia, the mix¬ ture being applied on the corresponding surface and a negligible amount of ammonia being passed over it. Curing proceeds from the outside to the inside and the curing agent is regenerated many times. EXAMPLE 3 A composition just like in example 2. The material to be impregnated by placing it for 10-15 min. in a 15-20 % ammonia solution. After squeezing the material is coated with the im- pregnatlng mixture and the curing process takes place from the inside to the outside. EXAMPLE 4 A two-pack mixture consisting of: Pack I 100 pbw of a polysulfide (LP-32C) 10 pbw of zinc oxide as acceptor of sulfur 5 pbw of titania as acceptor of superfluous alkalinity 10 pbw of lamp black , a reinforcing filler containing adsorbed CO and 0_. 20 pbw of an inert filler This mixture needs no preliminary drying of the components and noo storage in hermetical containers. Pack II 15 pbw of an aqueous solution and 3 pbw Na ^ ZnO. or 1 pbw NaOH oro catholyte with 0.2 pbw NaOH The composition solidifies very quickly after mixing the two packs. EXAMPLE 5 A two-pack composition consisting of: Pack I 100 pbw of a polysulfide polymer (LP-541) 30 pbw of amorphous S10 2 , a filler and acceptor of alkalinity Pack II 10 pbw Ca(0H) 2 , a regenerizing curing agent 10 pbw zinc oxide, acceptor of sulfur 15 pbw of water, a polar solvent The two packs are mixed before use. EXAMPLE € A two-pack composition coonsisting of: Pack I 100 pbw of a polysulfide polymer (latex) prepared in known manner and having the formula -(RS χ )- , wherein R = CH 2 -CH 2 -0-CH 2 -0-CH 2 -CH 2 S is a polysulfide linkage x is 2,3 or 4 n is about 500 with a molecular weight of 100 000, a sulfur rank of 2.3 and cross linking 0 % 30 pbw water remained after washing and filtering the latex 10 pbw of sodium polyacrylate, a latex stabilizer and a weak curing agent and cocuring modifier 50 pbw of a filler (lamp black and/or amorphous Si0 2 ) Pack II 50 pbw of a polyurethane prepolymer containing 8 % free NCO groups and solidifying during hydrolysis; the said copolymer is a commercially available product obtained from polyether-polyol and organic diisocyanate and has the following approximate formula: -CH CH - 5 pbw Hg(OH) , an acceptor of C0 2 evolving during hydrolysis of polyurethane 7 pbw Zn(Mn0 4 ) 2 .6H 2 0, an easily water-soluble curing agent for the polysulfide polymer 5 pbw Ca(Mn0 4 ) 2 .5H 2 0, a curing agent for the polysulfide The two packs are mixed before use. EXAMPLE 7 A one-pack curable mixture consisting of: 100 pbw of a polysulfide polymer, LP-31 being used for the example 10 pbw of zinc oxide, an acceptor of sulfur 10 pbw (NH 4 ) 3 [Fe(C 2 0 4 )/ 3 ].3H 2 0, a curing and gas-forming agent, easily water-soluble, decomposing at 165°C. 5 pbw N = C/NH 2 /N = C/NH 2 /N = COH (ammelite), a curing and gas-forming agent 5 pbw NH_COCONH 2 (oxamide), a curing and gas-forming agent 10 pbw MgCO. or dolomite, a filler and a gas-forming agent 3 pbw glycerol, an acceptor of moisture The mixture is cured under the effect of atmospheric moisture. EXAMPLE 8 A complex three-pack curable mixture intended mainly for thermal insulation, watertight surface insulation and atmospheric attack- resistant insulation with a high surface smoothness, a complicated shape and dimensional precision, consisting of: Pack I 100 pbw of a polyurethane prepolymer (just like in Ex. 6) containing about 8 % free NCO groups, solidifying during copolymerisation with mercaptothiopolymer or during hydrolysis and forming a coating layer with a low heat conductivity. 10 pbw of a polysulfide polymer, LP 32C in this example 30 pbw of ammonium ferioxalate, a crystalline hydrate, an easily water-soluble curing agent for the polysulfide polymer as well as a gas-forming filler. This mixture is applied as the first layer of the coating, the components being preliminary dried and homogenized under vacuum. Pack II The mixture is an aqueous desaggregated suspension consisting of components capable to decompose under a heating at temperatures from 50 to 500°C as well as to absorb the C0 2 evolved during the hardening of the polyurethane from Pack I, and forming the corre¬ sponding carbonates which also decompose at 50 - 500°c, the said mixture consisting of: 10 pbw of water, which is a dispersing agent for Zn(OH) and Mg(OH) 2 , a hydrolysing agent for the polyurethane, and a polar solvent for the curing agents. 5 pbw of Zn(OH) 2 , which is an acceptor of C0 2 and a curing agent for the polysulfide from Pack III 5 pbw Mg(OH) 2 , an acceptor of C0 2 1 pbw of NH 4 OH, an acceptor of C0 2 and curing agent for the polysulfide from Pack III. The mixture from Pack II is applied as a second layer of the coating. Pack III 100 pbw of a polysulfide copolymer (same as in Ex.l) 10 pbw of zinc oxide, an acceptor of sulfur and filler 10 pbw of asbestos powder, a filler retarding burning 10 pbw ZnC 2 0 4 .2H O, a gas-forming filler decomposing at 100 °C. 15 pbw of water, a structure forming reagent during the curing of the polysulfide copolymer, a polar solvent of the CA from the second layer. The mixture from Pack III is applied as the third layer of the complex coating. Preliminary curing of the third layer with NH 3 and subsequent sticking it to the first two layers is possible in cases when exact dimensions, a complex shape and a smooth surface are required. EXAMPLE 9 A one-pack compostion to be cured at elevated temperatures ranging from 150 to 200°C, the said composition consisting of: 100 pbw Thiokol ST with an average molecular weight of 40000, an average sulfur rank above 2.25 and cross-linking 0 % 5 pbw Thiokol LP 32C with blocked SH groups as a plasticizer, a curable polysulfide polymer. 5 pbw of zinc stearate (or nickel stearate or copper stearate) as a lubricating agent, a curable agent and a structure forming agent which saturates the valencies at the polysulfide bridges that have been liberated during the curing with stearate radicals, and decreases the volumetric expansion of the cured composition, re¬ spectively, when it is placed in solvents. 3 pbw of zinc oxide, an acceptor of sulphur and a curing agent. 5 pbw of Sn(C 3 H ? ) 4 , a liquid with a boiling point of 228°C, a dispersing agent of zinc oxide, a curing agent and a structure forming agent. 3 pbw of a polysulfide monomer (according to the given for¬ mula), a modifying agent. 50 pbw lamp blask, a filler, a support of adsorbed gaseous curing agent. The composition is prepared and cured in known man¬ ner. EXAMPLE 10 A one-pack composition to be cured at 150 - 200°C, which consists of: 100 pbw of Thiokol FA (average molecular weight of about 200 000) 5 pbw Thiokol LP 541 with blocked SH groups 5 pbw of zinc stearate 3 pbw of zinc oxide 5 pbw of (C 2 H 5 ) 3 SnSn(C 2 H 5 ) 3 , a liquid with a decomposition temperature of 270°C. 3 pbw of a polysulfide monomer, a modifier 50pbw lamp black and up to 10 pbw of other known fillers and special-purpose additives. The composition is prepared and cured in known manner. References 1. U.S.A. patent No 3225017 2. U.S.A. patent No 3951898 3. U.S.A. patent No 4608433

Claims: C L A I M S 1. A curable polysulfide composition comprising a poly¬ sulfide polymer or copolymer, a curing agent, fillers, plasti¬ cizers and other special-purpose additives, the said composition containing at least one polysulfide polymer and/or poly sulfide copolymer having a molecular weight of about 2000 to 200000, a SH - and SSH- groups content from 0 to 4 mol % , a polymerization degree of 10 to 500, in an amount of 90 to 110 pbw having the average formula R ! " / aT*- R Vy wherein S represents a divalent polysulfide or monosulfide radical x is an integer ranging from 1 to 6 a., a 2 and a 3 are the same or different and have values from 0 to 1. y has values from 1 to 10 y' has a value from 0 to 1 y" has a value from 0 to 5 z has a value from 10 to 500 1 has a value from 0 to 5 b has a value equal to the degree of polyvalency of R' minus 2 R is a saturated divalent radical selected from the group consisting of: - C n H 2n-> "C 6 H -' - C n H 2n OC n H 2n^ "C n H 2n SC n H 2n-» - C n H 2n C 6 H 4 C n H 2n' - C 6 H 4 OC 6 H 4- - 6 H 4 OC n H 2n-> - C n H 2n C 6 H 4 OC 6 H 4 C n H 2.T '> - C 6 H 4 0 C m H 2m 0 f C 6 H 4-' * - C n H 2n 0 C m H 2m 0 f C n H 2n~' - C n H 2n OC 6 H 4 OC n H 2n-' -CH2--CI6.H3--CH2,-; -CH2_-CιH-CH2.-; CH 3 CH 3 C 6 H 5 - 1.8- -cellulose-OC wherein n ranges from 1 to 24 m ranges from 1 to 5 f ranges from 1 to 10 " t R'* and R ϊv are the same or different saturated monovalent hydrocarbon, oxahydrocarbon or thia- hydrocarbon radical R v is a saturated monovalent alkyl radical of the kind "SC m H 2m+l ° r - 0C m H 2m + l- x is a polysulfide linkage; ranges from 3 to 5. R., and R 3 are the same or different terminals representing normal or iso-alkyl, aryl or aralkyl radicals or groups of the type: -SH; -SSH; -OH; -CHO; -C n H 2n+1 ; -C n H 2n C 6 H 5 ; - C 6 H 4 S 6 H 5' " ∞A' " ∞Ao' " ∞A∞Aa l* - C n H 2n 0H ? ~ C 6 H 4 OH ' -° C 6 H 4 C 6 H 4 OH? "0C n H 2n 0H ' -° C n H 2nV NHC 6 H 5 ? CH^CH-CE^ -CH-CH 2 -CH-CH 2 ; V OH R° R° I -C nH 2.n-S ,i-R « ; -C nH 2,n/OC mH, 2m /. l-Si-R" ; R ooo R° I -CH--CHCH„/OC Em, /- -Si-R°° ; i. j 2 m 2m x. I OH R 000 wherein R°, R°° and R°°° are the same or different saturated monovalent radicals of the group κ : -OCmH2_m J +_l; - 1.9 - -OC mH 2,m C 6-H 5, or -C mH 2.m+ 1 l n has values from 1 to 10 m has values from 1 to 5 1 has values from 1 to 10 R' is a polyvalent radical with a weight up to 10 % from the molecular weight of the said polymer or copolymer and is a radical of a polyfunctional com pound selected from the group: XR,X 2 ; XCH 2 CHXR„CHXCH 2 X; R f J ,CX 3 ; R IV X 4 ; CH 2 CHCH 2 X; 0 wherein XX is a halogen atom R and R JJJ are hydrocarbon, oxahydrocarbon, thia- hydrocarbon or aralkyl radicals Rx is selected from the group consisting of alkyl, aryl, aralkyl radicals or is a carbon atom R,* R VI , R^ j , K„ τ , and R„ are alkyl radicals representing a hydrocarbon or oxahydrocarbon R°, R ∞ and R°°° are the same or di ferent monovalent radi¬ cals of the group: ~∞ - 2m+1 . -C^C g H,. -OC fi H 5 , wherein „ " ranges from 1 to 5 and , J, n* ranges from 1 to 10 R" represents a saturated divalent radical free of SH, SSH and S groups and is selected from the group: -CH-CH-CH- -CH.-CH- -CH -CH- ; ^ I OH CN C 6 H 5 -CH 2 -CH a CH 2 OCH 2 CH 2 CH 2 Si/OC m H 2m / 2 - ; -CH 2 -CH- OCH 2 C 6 H 5 -CH 2 - ^C-CH-CH j O/CH ; , , OCO-HN MH-COO/CH,/^ OCH j -CH-CH, OH H 3 C -<o - NHCOO CH j / j OCONH -<^ Q ^>- CH, I -CH 2 -C jH-CH 2„-0 ~<T θ >-C i-< >- O-CH 2 ,-C „H-CH_ 2- OH R°° OH wherein m has values from 1 to 5 1 1 has values from 4 to 6 1 2 has values from 4 to 6 R° and R°° are the same or different having the corre¬ sponding meaning of R°, R°°, R 000 included in R, or they are hydrogen atoms or alkyl radicals and the said composition comprises as well: a modifier of up to 75 pbw a curing agent of 0.2 to 20 pbw a polar reagent and/or solvent of up to 25 pbw an acceptor of 5 to 50 pbw fillers and other additives of up to 150 pbw. 2. A curable polysulfide composition as set forth in claim 1 the modifier represents a polysulfide polymer free of -SH and -SSH groups, the said polymer having a molecular weig ght of up to 2000, a degree of polymerization of 2 to 10, a sulphur rank of 2.5 to 5 and the general formula wherein is a polysulfide linkage x has values ranging from 2 to 6 y has values from 3 to 10 a is from 0 to 1 R, R and R 2 have the meaning of the corresponding radicals according to claim 1. 3. A curable polysulfide composition as set forth in claim 1, wherein the modifier is a bis-polysulfide dimer with a general formula of the type wherein S χ is a polysulfide bond x is an integer from 3 to 6 R is a saturated monovalent radical free of -SH and -SSH groups and is selected from the group consisting of: -S- 0C m H 2m + l ' ' - Vc l 011 CH-CH. (CH 3 ) 2 wherein to R- 4 denote alkyl or aralkyl radicals containing from 1 to 15 carbon atoms; R°° and R°°° are the same or different saturated monovalent radicals of the kind "0C m H 2m+l -° C m H 2m C 6 H 5 - C 6 H 5 ~ C m H 2m+l wherein has values from 1 to 5 1 has values of 1 to 5 P has values of 1 to 5 Ar is an aryl radical Or R belongs to the group of benzothiazoles or another modi¬ fying group, or the modifier represents a monomeric polysulfide, of the kind where S is a sulphur atom; S χ is a polysulfide bond; x is an integer ranging frommm 3 to 6; R 2 , R 2 , R 3 and R 4 are the same or different monovalent modifying radicals having mostly the meaning of radical R of the polysulfide dimer proposed. 4. A composition according to claim 1 wherein the modifier represents a hydrolyzable polymer or a polymer able to copolymerize with a mercaptan terminated polysulfide polymer or is polymer covulcanized with a polysulfide polymer free of -SH and - SSH terminals 5. A composition according to claim 1 wherein the modifier polymerizes and/or copolymerizes and/or cocures with the basic polysulfide polymer or copolymer, and the said modifier is any one of those claimed in claims from 2 to 4 is a combination of some of them. 6. A composition according to claim 1 in which the curing agent interacts and/or dissolves at the curing temperature in a liquid or gaseous polar reagent and/or polar solvent and is se¬ lected from the group consisting of: gaseous substances; ammonium hydroxide; hydroxylamine, hydrazine; organo-hydrazines; ammonium and metal raonosulfides; metal powders, oxides, hydroxides, carbon¬ ates and baβic salts; complex hydroxides; carbonates and oxalates; ammonium and metal salts of metal acids (double oxides); metal pyrophosphates; complex metal cyanides; alkali catholytes; metal alcoholates, polyalcoholates and polymeric alcoholates; metal mercaptides and polymercaptides; salts of mono, di and tricarboxy- lic acids and their derivatives; polymeric carboxylates; metallio- organic hydrocarbons including naphthenates and octoates, phos- phonates, thiophosphonates, borates, boranes, sulphonamides etc; metal amides; organic amides and amines; organic aldehydes; alkalized chloroparaffins, chloropolyphenyls; unsaturated low-molecular weight compounds etc; or the said curing agent is stable in the used polar solvent and is a metal powder, oxide, hydroxide, oxahydroxide or salt whose metal has a higher chemical affinity towards oxygen or the exchangeable anion, or the said curing agent is an ionic melt or a metal containing polar liquid or is a combination of two or more of them. 7. A composition as set forth in claim 1 wherein the polar reagent and/or polar solvent of the curing agent is in liquid or gaseous form at the curing temperature. 8. A composition according to claim 1 wherein the acceptor is an acceptor of gaseous polar reagent and/or solvent and repre¬ sents an organic liquid infinitely soluble in the said solvent or is a strongly hygroscopic potential curing agent or is a combina¬ tion os some of them. 9. A composition according to claim 1 wherein the acceptor forms a solid-phase metal-containing compound which is stable in the used polar solvent and represent an acceptor of sulphur or an acceptor of CO , or an acceptor of acidic anions, or an acceptor of excess of alkalinity or is a combination of some of them and acceptors according to claim 8. 10. A composition according to claim 1 wherein the gas-forming filler decomposes at temperatures of from 50 to 500°C and represents mainly a crystalline hydrate of a complex ammonium hydroxide, carbonate or oxalate, while the w active" filler con¬ tains an absorbed, adsorbed, activated or ionized curing agent. 11. A composition according to claim 1 in which the special- purpose additive is an inhibitor of curing and represents a chemical compound binding the active atoms and/or ions of the curing agent to moderately or weakly active atoms and/ or ions and is mostly polyol, carboxylic acid, boric acid, their derivatives or mixtures etc. 12. A composition according to claim 1 and a method of curing the said composition at ambient temperature by the said method, by which one-pack composition deposited in the corresponding place is cured by surface contact with a gaseous liquid or dissolved curing agent and/or a gaseous or liquid polar solvent or their mixtures, while the two- and three-pack composition is cured by layer- by-layer application.

Inventors: ORECHAROV PETKO LUBOMIROV, ORECHAROV ROSSISLAV LUBOMIROV, ORECHAROVA LILIANA STANIMIROVA, VASSEV EMIL STOILOV, ORECHAROV, PETKO LUBOMIROV, ORECHAROV, ROSSISLAV LUBOMIROV, ORECHAROVA, LILIANA STANIMIROVA, VASSEV, EMIL STOILOV
Applicants: ORECHAROV ROSSISLAV LUBOMIROV, ORECHAROVA LILIANA STANIMIROVA, VASSEV EMIL STOILOV, ORECHAROV, ROSSISLAV LUBOMIROV, ORECHAROVA, LILIANA STANIMIROVA, VASSEV, EMIL STOILOV
Application year: 1994
Main classification: C08L81
IPC codes: C08G18, C08G59, C08G75, C08K3, C08L81, C09D181